locrian (Hive Bee)
04-17-02 08:19
No 298039
      Oxime route re-working ...  Bookmark   

I'm just curious.  The Oxime route kinda sucks.  Swinl followed this recently: 

54g sodium carbonate and 40ml water was combined in a 500ml round-bottomed flask. The mixture was heated gently with stirring until the acetate was in solution. 200 ml MeOH was added followed with 45g MDP2P. To this there was added 23g hydroxylamine hydrochloride and the mixture was refluxed with stirring for 1.5h. After this period 10ml water was added and the heating source was removed and the mixture was allowed to cool in a waterbath with the stirring continued. After returning to room temp the flask was put in the freezer for an hour or so. The white crystalline material was filtered and washed with 500ml water (the filtrate may turn cloudy as small amounts of product crystallizes). The product was dried over magnesium perchlorate. Final weight was 41.4g (92%). Mp: 84-85C. Litt: 84-87C (H2O-EtOH)

Then ....

In a 4l beaker with mag stirring, 0.75 moles of activated Al (19.5g) [2] is added to 1l 95% EtOH and 100mls dH2O, followed by 0.33 moles oxime of MDP-2-P (65g), and 3 moles HOAc (180g). The Rxn is heated to 60C and heat removed. There follow three additions of 0.75 moles of activated Al at 30 minutes, 1 hour, and two hours. Temperature was maintained at 60C by placing beaker in a cold water bath as necessary. There is a vigourous evolution of hydrogen as the rxn progresses, care must be taken the rxn vessel does not overflow. An additional 150mls 95% EtOH and 15mls dH2O is added at 2hours. At 3 hours the rxn is a viscous gel which has stopped the stir bar. An additional 300mls 95% EtOH and 30mls dH2O is added . The rxn was allowed to stir until it has returned to room temperature, during which time 1 l of 15M NaOH was prepared and cooled. The rxn vessel was placed in a cold water bath and the basic solution was added slowly over 20 minutes, with care being taken the tempertaure did not rise above 60C. 500g of NaCl was added, much of which precipitated after stirring. 500mls toluene is added with stirring. The toluene/EtOH/amine layer is separated and decanted into 750mls of dH2O, causing the EtOH to migrate to the aqueous layer. The toluene layer is separated and the aqueous/alcoholic layer is extracted 2 times with 250mls toluene. The pooled toluene extracts are washed
once with 400mls dH20 and once with 400mls brine, then driied through MgSO4 and gassed w/ dry HCl gas.

yeild 0.267 moles MDA.HCl (54g) 81% molar yeild

1) see Post No189985 2) activated by refluxing in 19.5g Al in 800mls of 50/50
dH2O/MeOH, with 1g HgCl2 for 15 minutes, the mercuric solution was decanted, and
Al was washed once with 400mls 95% EtOH, which was also decanted. Same mercuric
solution was used for all four activations.


The whole thing is sort of clumsy and haphazard IMHO.  How could this be shaped up?  I'm thinking something like MM's Nitro/Al/Hg thing.  Same concept.  Could the oxime be formed and then subsequently reduced all in the same pot, like as soon as it precipitates with the Hyrdoxolymine somehow? 

Let's say you run MM's amination, but throw out the NitroMethane and have ~12g Hydroxylamine in the pot already mixing.  Would Ethanol be advantageous to use instead of Methanol as discussed before?  I never saw why, but what do I know?  The Nitro sort of boosts up the reaction, but with some initial external heating, the same effect could be achieved no?  I don't know much about chem., never pretended to, just curious from a functional viewpoint, dig?

We need new drugs.
 
 
 
 
    Vibrating_Lights
(Hive Addict)
04-17-02 09:03
No 298058
      oxime  Bookmark   

To reduce the oxime with decent yeilds via AL/HG the rxn must be acidic.  For the formation of the oxime freebase hydroxlamine(basic) must be used.  however i suppose you could make the oxime in baisc EtOH then add the GAA to the resulting mixture followed by the slow addition of the preamalgameted AL. Any leftover hydroxlamine could end up in your final product though unless you care to distill the freebase(you could probably suck it off with vaccume.  The formation of the oxime is done as a seperate step so that the unreacted hydroxlamine can be washed away from the oxime.  Also the nitro causes excessive heating because there are 2Oxygen atoms on every molocule to reduce.  The reduction of the oxime does not produce much heat cause there is really only the O from the ketone to reduce.
VL_
 
 
 
 
    locrian
(Hive Bee)
04-17-02 09:41
No 298075
      Reply to 'oxime'  Bookmark   

Okay, fair enough on the oxime being separate then.  This I understand.  And then washing it makes sense, but I think swinl lost yield in this part.  Swinl didn't weigh the tone though, was too afraid, it looked like less than what swinl thought it should look like.  Swinl'l have the results soon enough.  An A/B would just take the Hydroxylamine with it I suppose, right?  It's the last part.  Why not throw everything together and reflux it in two batches in two 2L's?  No pre-activated shit either, throw the whole shebang together and let the whole thing go down right there.  Could the oxime be dissolved in something and dripped in?  Probably wouldn't matter w/out the Nitro, so I think you could drop eveything in together, 27.5g of Al, 400mg of HgCl2 to ~20g of oxime.  What about ethanol?  Must this be used instead of methanol?  I'd guess ~600mL ethanol or maybe ~800mL methanol.  Prepare the foil with the grinder like with MDMA. 

Also, is there a better way to remove the hydroxylamine?

We need new drugs.
 
 
 
 
    Vibrating_Lights
(Hive Addict)
04-17-02 11:30
No 298112
      ethanol  Bookmark   

The ethanol AA mix was found to be the highest yeilding.  AB2 tested it extensivly.  The best part about the rxn is that there is not to much heat produced. Not even enough to boil the solvent and there is no amine smell as the amine is already attached and there isn't excess to get into the air.  As for the Al just put some Hg salt in some MeOH in a tupperware container with the al and use a cooking spoon to add it. you probably might be able to get away with adding it all at once if you were to use a bucket.  the only thing limiting you here is the relese of H2 that will cause the rxn to possibly foam over.
VL_
VL_
 
 
 
 
    Antibody2
(Rehabilitated)
04-18-02 04:03
No 298426
      here's the shit  Bookmark   

Post 298425 (Antibody2: "Al/Hg/HOAc Oxime redxn", Methods Discourse)
 
 
 
 
    locrian
(Hive Bee)
04-19-02 13:32
No 299070
      Reply to 'here's the shit'  Bookmark   

Yes, we got that, and major kudos.  But!  Can there be a simpler way to do this?  Swinl doesn't like the activating of the tinfoil.  Is this necessary or can it be done sort of all at once a la Nitro/Al/Hg amination?  If not, why?  I guess its not that big of a deal, it would just seem easier and safer to me.  Swinl hates mercury. 

BTW - interesting to note this part in AntiBody's writeup(which swinl didn't know).

It should also be noted that the following solvent/redxn system was sucessfully employed in the manufacture of MMDA and DMMDA but in lower yeilds, 10% and 50% respectively. It failed repeatedly with DMMDA-2 altogather.

But recent shit I've read seems to suggest that the method will work and that DMMDMA-2 could be worthwhile.  Maybe it'll be like the new mescaline - just need to take a lot. (?)


We need new drugs.
 
 
 
 
    Antibody2
(Rehabilitated)
04-19-02 15:11
No 299083
      try to fit 80g of foil into one litre of solvent, ...  Bookmark   

try to fit 80g of foil into one litre of solvent, its a problem. The rxn would also be more exothermic, and all the hydrogen evolution is problematic. For smaller rxns fine and dandy.

Osmium would probably tell you, use thicker foil or Al sheet. . .

i get the impression tho loricran you want the dope to make itself and land on a platter for you.
 
 
 
 
    locrian
(Hive Bee)
04-19-02 17:50
No 299110
      Reply to 'try to fit 80g of foil into one litre of  Bookmark   

i get the impression tho loricran you want the dope to make itself and land on a platter for you.

you said it, brother.  dope that makes itself ...now that would be the ultimate drug. (sigh)

We need new drugs.